1. Field of the Invention
This invention relates to a method of producing a 3-substituted-2,2-dimethylbicyclo[2.2.1]heptan-5-ol of general formula (I): ##STR1## wherein Z is .dbd.CH.sub.2 or ##STR2## or a lower fatty acid ester thereof. More particularly, this invention relates to a method of producing a 3-substituted-2,2-dimethyl-bicyclo[2.2.1]heptan-5-ol of the above general formula or a lower fatty acid ester thereof which comprises subjecting tricyclene or/and camphene to electrolytic oxidation in a lower fatty acid and, if necessary, further subjecting the oxidation product to hydrolysis and isolating the resultant 3-substituted-2,2-dimethylbicyclo[2.2.1]heptan-5-ol of general formula (I) or lower fatty acid ester thereof.
In another aspect, this invention relates to a perfume, fragrance composition containing 2,2-dimethyl-3-methylenebicyclo[2.2.1]heptan-5-ol of general formula (I) wherein Z is .dbd.CH.sub.2 or/and a lower fatty acid ester thereof.
2. Description of the Prior Art
2,2-Dimethyl-3-methylenebicyclo[2.2.1]heptan-5-ol of general formula (I) wherein Z is .dbd.CH.sub.2 is a monoterpene alcohol which was isolated by Matsubara et al from the essential oil of Chrysanthemum japonense, and is known as nojigiku alcohol [Tetrahedron Letters No. 48, 4219-4222 (1974)]. It is known that nojigiku alcohol can be synthesized by chlorinating camphene with chlorine gas, followed by reacting the chlorinated camphene with potassium acetate, and finally hydrolyzing the obtained acetoxy-compound [D. L. Dull et al, J. Org. Chem. 29 3095 (1964)]. However, this process is not fully satisfactory from the viewpoint of yield, selectivity, etc. It is also known that camphenilane aldehyde, borneol, 2.beta.-camphenilyl alcohol, etc. can be produced by subjecting camphene or tricyclene to electrolytic oxidation in the presence of lithium acetate as a supporting electrolyte using stainless steel electrodes [Matsubara et al, Synopsis of the 16th Symposium on the Chemistry of Terpenes, Essential Oils and Aromatics, 111-112 (1972)]. However, such electrolytic oxidation or saponification is not known to give nojigiku alcohol or an ester thereof.
Cyclic monoterpene alcohols and their esters such as borneol, isoborneol, bornyl acetate, isobornyl acetate, etc. have distinct fragrances characteristic of conifer wood and have been used for cosmetic preparations, bath preparations and toiletries, room sprays, etc. but it is not known that nojigiku alcohol is useful as a perfume, fragrance material.
It is an object of this invention to provide a novel method of producing a 3-substituted-2,2-dimethylbicyclo[2.2.1]heptan-5-ol of general formula (I) or a lower fatty acid ester thereof.
It is another object of this invention to provide a method by which nojigiku alcohol or a lower fatty acid ester thereof, which is useful as a raw material for the production of floral scent fragrances, can be easily produced.
It is still another object of this invention to provide 2,2,3-trimethylbicyclo[2.2.1]heptan-3,5-diol or a lower fatty acid ester thereof, which is a novel compound of value as a synthetic intermediate for the production of nojigiku alcohol or lower fatty acid esters thereof, and a method of producing said diol or ester thereof.
It is a further object of this invention to provide a perfume, fragrance composition containing nojigiku alcohol and/or a lower fatty acid ester thereof.
These objects as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.